Production of alkyl glycosides



PRODUCTION 0F ALKYL GLYCOSIDES i @M+ JMW;

Dec. '1 1, 1945. M CAN-TOR 2,390,507

PRODUCTION 0F ALKYL GLYCOSIDES Filed Jan. 2l. 1941 2 Sheets-Sheet 2.50007014575 fracasa 6?:

MM@ @SM-2@ Pe vzdlsiy Can/? Patented Dec. 11, *19t-l5'4 Sidney M.Cantor, Riverside, Ill., assigner to Corn Products Refining Company,4New York N.' Y... a corporation of New Jersey' Application January 2l.,194:1,` Serial-lilo'.V 375,288

(Cl. 26h-27170 Y 25 Claims.

This invention relates to, and has for its object', the production of,alkyl glycosides directly from reducing saccharide polymers. Methylgl'ucosides have been produced by heating powdered glucose with methylalcohol, containing hydrogen chloride, and crystallizing the solution.(Emil Fischer,` The Compounds of Sugars with Alcohols and Ketones,Berichte 23, 1145-1895, Collective volume I, pages T40-741i. The processdescribed is an anhydrous operation. The same article states that starchmay be treated in the same way to give alpha methyl glucoside.

One of the objects of the present invention is to produce'from starch,dextrine or other reducing4 saccharide polymers. non-crystalli'zableSyrups consisting, dry substance basis, of a major quantity of aglucoside (ethyl, propyl, butyl, amyl) and. a minor quantity of reducingsacchai'ide polymer glycosides, together with, optionally, a smallquantity of a reducing sugar. These syrups may be used, effectively, asplasticizers for animal glues, in the place of corn syrups, which latterhave a tendency to react with and so tan or cure the protein material inthe glue, which is not the case with the glycoside syrups. Furthermore,the glycoside syrups of this invention, particularly those produced bythe higher alcohols such as propyl, butyl, or amyl alcohols, have thecapacity of lowering. the surface tension of liquids, such, forexample,. as the oil and water emulsions used` in the lubrication ofmachine tools.- 'Ihe ethyl glucoside syrups are non-toxic so they maybeused in food products.

A further object of the invention is to facilitatethe reaction betweenthe alcohol (including also methyl alcohol) and the starch or otherreducing saccharide polymer, to increase yields, by using in thealcoholyss converting operation substantial quantities of water-theusual processes being carried out under anhydrous conditions-thereby,also, avoiding the expense and inconvenience of employing anhydroussubstances.

The term glucoside includes a dextrose or glucose compound wherein thehemi-actal hydroxyl of the aldehyde group of the dextrose molecule hasbeen replaced with an organic radical such as a methoxyl, ethoxyl orother alkoxyl group. The broader term glycoside" includes any. reducingsaccharide compound wherein an organic.V radical has been attached tothe carbonyl carbon through oxygen.v

The term polymer of a reducing saccharide includes, in addition tostarch, the preferred dextrose polymer employed aslraw material forapplic'antsinvention, the' polymersloi' the' aldoses'.- suchl forexample-v a's dextrl'zie-,- cellulose; and lichenm; which are polymersof? dextrose,` the' polymers' off' th'e ketoses; s'uchasinulinfwliich-lis a polymer' of le'vulose or fructose;4 thepentosanswhich aref the polymers off the pentc'ases,V e'. g.- a-rabinose' and'icylose'; thepectins, e.A g. aigaragar and gum arabic, which-are' thecondensation productsv ofgala/ctose or' arabin'os'ewithA galasturonic'acl'dsz: the: disa'cluafride's;` such` as'l sucrose,-v maltose, lactose,cellobi'ose 92ndgentiobiose, which by' hydrolysis'- yiel'd simplereducing sugars;- and also the polymers of reducing'lsugar acids ofwhichI thereV are'A a; very' large numben Every reducing sugar ca'fn'-be'l oxidized to an: acid, the character of which dependsl uponthecarbon atom on'- which oxidation takes-- piace anri-V upon thenature' of` the group attached such; carbonl atom; whetherV a' hydroxylgroup, an aldehyde group or other group Thepro'cesslo'f the presentinyention may' be applied;- for example, tothe polymers of glucuronicacid, derived from' dextrose, which acid has an ald'ehyd'e group' inIits molecule' anclis therefore a: reducing sugar acid. The pectinsAwhich' are polymers ofgelach turonic acids are: to be= included4 withinthe term polymers off reducing' saccharides Whichl term comprises, ofcourse-,nieny` other substarice'sl not specifically named; In fact, anymatel'flal'y may; inI theory `at least, b'e subjected tio" thereactibnof the present invention tov obtain aL glycoside, provided the' materialis-of= a character to b'e'- com vertedI by' an' a'cid toa substancecontaining. reducingsugars or reducing sugar acids;A

In accordancewithi the present inventionthe selected polymer' of a*reducing' saccharide" is reacted withan' aliphatic compound' containingalcoholic l'n'mlrcxyl group, which is-hydrophyll'c; i. e. rniscibleIwholly' or in'A part' with water; For prac-tical purposes,- in' orderthat the yield'may be sufc'ient to make theA process worth while; thesecompoundsshould not contain more than fiveV carbon atoms. This groupA ofcompounds comprises: moh'ohydric alkyl alcohols', e. g: methyl alcohol',ethyl alcohol, normal1 and iso propyl alcohols, the butyll` alcoholsandthe amyl alcohols; It also comprises the' polyhydricalcohols, such asthedihydric'group, including' the glyco'ls and the- `tr'lhydric` groupincluding glycerln'e. lt also includes" aliphatic` compoundscontainingalcoholic hydroxyl groups and acid g1 oups` e. galactic, tar-tarde andcitrikaci'dsz also aliphatic compounds containing alcoholirs hy'- droxylgroups and amino groupssuchc asunono. di@ or' tri-ethanol* amine: also'Icompounds con taining alcoholic hydroxyl groups and aldehyde groups suchas glycolic aldehyde and glyceralde' hyde. The compound may be said toconsist of or Ito contain an ROH group in which OH represents analcoholic hydroxyl group and R represents any alkyl radical; althoughfor practical purposes, and considering yields, it should be onecontaining not more than live carbon atoms.

'Ihe catalyst used may be any acid which does not decompose thecarbohydrate. This will exclude nitric acid, at least in most cases. Themost desirable acid is hydrochloric acid because it delivers thegreatest number of hydrogen ions per unit volume of the acid.

The reaction may be anhydrous. But this is not necessary or evendesirable in most cases. The presence of some water is advantageous (l)because it increases the activity of the acid, i. e. increasesionization and thereby increases yields; and (2) because it increasesthe susceptibility of the carbohydrate to the desired reaction byfacilitating the production of low molecular weight polymers, that is,intermediate conversion products, and this also leads to higher yields.However, the water should be present in such small quantities relativeto the quantity of the alcohol (or other ROH equivalent) that in thesolvolysis of the carbohydrate the alcoholysis excludes, cr

in any case, predominates over, hydrolysis. In some cases a certainamount of hydrolysis of the carbohydrate to reducing sugar may takeplace. In some of the examples to follow purities are given, meaningreducing sugar content calculated as dextrose, and this, of course,indicates some hydrolysis of the carbohydrate.

By describing the reaction as one involving the dlrectj production ofthe glycoside from the reducing saccharide polymer, it is not intendedto suggest that hydrolysis of the material at an intermediate stage ofthe process may not take place. What is meant is that no free reducingsugar is produced; except in some cases and in minor quantities as abovestated. If hydrolysis does take place, as appears to be the case, it isfollowed immediately by the alcoholysis without the Iproduction of freereducing sugar, in any considerable quantities at least. The alcoholysisis therefore the predominant reaction. The process of conversion of thereducing saccharide polymer to the glycoside is in eiect, therefore, aone step process not a two step process. The degree of intermediatehydrolysis can be varied from a mild hydrolysis, for example onecorresponding to the conversion of starch to glucose (in the commercialsense), to a hydrolysis corresponding to conversion to maximum dextrosecontent. Within this range of conversions the alcoholysis will bringabout the production of glycosides from the glycoside of the simplemono-sugar, dextrose to glycosides of high polymer reducing saccharides,e. g. the glycosides of reducing dextrines. Between these extremes therewill be glycosides of saccharides such as maltose and of trisaccharides.

The following are specific examples of reduction to practice of theinvention. It will be understood that these examples are purely typicaland informative and are not to be considered as limitlng the inventionto the specific operating data given. The intention is to cover allequivalents and also all modifications Within the scope of the heretoappended claims. In these examples the ranges, sometimes included inparentheses, are workable and practical ranges but not critical. Theparts and percentages are by weight unless otherwise indicated.

In the accompanying drawings: Fig. 1 is a dow sheet illustratingExample 1. Fig. 2 is a ow sheet illustrating Example 2.

Example 1.-Alpha methyl glucoside from starch with some water presentThis process is indicated, graphically, in flow sheet Fig. 1. The watermay be introduced with each of the ingredients of the batch, the starch,the alcohol and the catalyst or with any one of these materials, orindependently of any of them, as indicated by the dotted line 2E. Thepresence of 5% of water from any source is desirable in order to bringabout increased ionization and to effect the breaking down of the starchto lower molecular weight polymers. A larger amount of water, however,may be used Without hydrolysis resulting in the production ofsubstantial amounts of free dextrose provided the alcohol, or other ROHcompound is suiliciently in excess of the water so that alcoholysispredominates over hydrolysis. The theoretical amount of water necessaryfor hydrolysis is 11.1% based on the weight of the dry starch. But thisamount may be exceeded without producing any substantial amount of freedextrose, through hydrolysis, if the ROH compound is in sufficientquantity to make its reaction with the carbohydrate the predominantreaction. The process is preferably carried out as follows:

(a) parts dry substance starch containing about 12% of moisture, theusual moisture in commercial, air dry, corn starch, is mixed with 850parts of methyl alcohol, the usual commercial anhydrous methyl alcohol,a workable range being between 500 and 1000 parts, and 8 parts of 18Baume hydrochloric acid containing about 27% hydrogen chloride and thebalance water. The resulting methanol and acid solution will containabout 2.5% hydrogen chloride. The amount of water is in the neighborhoodof 18% based on the Weight of the starch. A practical range would befrom 15% to 20% of water, assuming 850 parts of anhydrous methylalcohol.

(b) This mixture is transferred to a converter-the converting vessel I0of Fig. l-which may consist of a vessel provided with a refluxcondenser, but for practical operation is preferably a steam jacketedpressure cooker. The suspension is heated to a temperature of G (222 F.)and maintained at this temperature for four hours. Possible ranges are65 C. (150I F.) for 45 hours up to 105 C. (222 F.) for 4 hours.

(c) The converted material is then ltered at II to remove unconvertedstarch.

(d) The material is then cooled at I2 to about 20 C. (68 FJ.

(e) The methyl glucoside is then crystallized at I3, the crystallizationbeing preferably a still crystallization, which operation requires about2-3 hours.

(f) The crude alpha methyl glucoside-about 90 parts by weight, drysubstance basis, is separated from the mother liquor by centrifuging asindicated at I4.

(g) The mother liquor, rst greens, containing 30 parts of methylglucoside, dry substance, is reconverted, filtered, cooled, crystallizedand centrifuged as indicated at I5, I0, I1, I8 and I9 (Fig. l) to give asecond yield of crude alpha methyl glucoside.

(h) The second greens from the centrifuging asco; ses

operanon Ware'reuimed totherst converting operatimrattil' 24 parts, drysubstance, is added to'tl'erst crudh methyl glucoside,. 90l -parts,.andv the material. dissolved at in ZSUpartls of methyl alcohol.

(i). The so-lution is decolorized at 2| with l part of 'Uarcoor"otheractivzalteclj caroonf and is nlti'ed' at' 22'.'

('ly *I'he'iiltrate`V is crystallized at 23` by' ailowv iiufittostandi'at' room' temperature for' fromi Zto 3 hours and isthencentnuged'at 21%' CD The thirdgreensfrom thislast 'centrifugingoperation are returned; preferably; t'othe* reconversion operation atf5.

(my Thehpure' aipi'rat methyl' giucoside-fiom the' lastcentrifugingoperation is dried at 'anrl" gives a'yfeltf of'102 parts;ryrsubstance Example ZLf-Producticm of beta methyl glucoside Tfiisoperation is disclosed graphicaiiyf inl the owsheet (Fig. 2); Theraw-materica is-therst green's from Example No: 1, that is, the greensl'romlthe centriuging operation at i4- (Fig` 1). The processispreferably' asl follows:

(i1-l" The-30 parts of drysubstance first greens is neutralized withanhydrous soda ash or other suitable neutralizingl agent; as indicatedat 2l (Fig. 2) to stop the conversion.

(b)- I'he neutralized. liquor is then filtered at 28.

(c) The ltrate is crystallized at room temperaturefortwo'to three hoursas indicated at 29.

(dir The'massecuiteis centrifugedat' 30; This gives* about 60% of the*30 parts dry' substance greens, or'lparts of drysubstance-, in t-hoformofcrude alpha methyl glucoside'which'- may be transferred to` thevprocess of Example-No; l and reflned"as described therein; v

(e)= The greens froin the centrifuging loperation .'itlare concentratedat 3-I to about 85 Brix.

ffl' "Ihe liquor is' then cooled at 3-2 to about room` temperature.

(17)' The' cooled liquor is crystallizedV for about three-hours asindicated at 33'.

(Vi-Y 'Ihe'mass'ecuite''s' centrifuged'Y at 34 givingbeta;niethylgiucoside'inl an amount of about 8.4 parte` dry' substance.

Gib'- 'I'hefgre'ens fromtnecenbrifuging operation :ill'm-tlii'rcllgrEensP-are concentrated at -36V to'I about 85 Brlx.

(i) The. concentrated liquor is crystallized at 36.

(ki The massecuiteis centrifuged at 3l giving about 1x2 parts' ofsecond' beta methyl glucoside dry substance.

(l)' The' fourth` greens from the centrif-uging operation 31 arepreferably discharged-A fromA the system. The se'con'd crude'beta;`methylglucoside is added to the first crude beta methyil glucoside anddissolved at 38' with' 25 parts of1 methyl alcohol;

(vrt) The'solutionis'crysta'llized at 39 for about threehours.

011) The-massecuite is centrifuged at 10 giving '712V` parts pure betamethyl glucoside dry substance.

(bl Thealcoholic solution from the-centrifuglng operation at 40 isreused, preferably, in the concentrating operation at 35'.

Example 3.-Ethyl glycoside syrup from starch 2500 parts of: air' drystar-chy is mixed, with 13,000 parts (10;000 to'15,000parts)f of 95%ethyl alcohol and 982 parts of 18 Baurn hydrochloric acid. 'i'iel actuarcriterion: is not' thef weight es the acid'iiitituei percentage esacidityor fthere suitii'g'f afcohelwcic seiutionf; 'Fhlsl acidity 'may'rangebetweenzK-and 5%.. FIief-Iafiaumeglxy: drochloric acid containsabout 27% of acid'and metaframe-water. 'Ififeir totai amount er waterwiiif lie't shoutA 70% based" cm1v the-starch; 8%n1oifstiiie' i'n the)starchi- This-'mixture ineen-f ver-ted a steam jack/@tealpressurefcooier; at' 31 to 45 geminis` steam'l per! square foraboutftiireefioursf- (Sitios hours. The teun peraturewitiiin ftheconverter liquor snouldbe approximately within? theratgefof 1.121* O,0234 F3* iio-l 118"C2- @MWFL Thefpressuref is: then:

released' and thefliquorneutraiized* sodium;

carbonate, caustic soda or any other suitahle alkaline material.preferably in dry form.. The liquor is then filtered,` decolorized bythe addition of 5% of Darco, based on the weight of the starch,

fliteredagainand evaporated tno-remove* the excess of ethyl alcohol.The' proi'iuctis a syrup-oi" ethyl gl'ycosides having'a purityy of 3%-(reducing sugar calculatedl as deirtrosel andA a? yield of' ethyl'-glycosides of 97%l on the of reducing' sugars produced By thereact'i'on,that is, the alcohol'y'sis is 97% eflicient. The syrup'isnon'crystallizable; and', because-produced by the'- use of`ethyl`alcohol', is' non-toxic anni can: be used in: food products. TheI purityindicates that a small amount of free reducing suga'nhas been producedby hy# drolysis'.

The nomi-educihg or gl'ycosid'e'dry substance of thesyrupconsists'ofabout 90% of ethyl glu coside and` about 10%of dextrosepolymer glycosides.

This syrup; tl'ieglycosidedry'substance-of which consistsof amaibrpnrtibn' of ethyl glucoside' an'd a minorportion" of' dextrosepolymer ethyl glycosides', is, it' ls believed', a newpro'duct.

Example 4.-Ethyl glycoside syrup from dextrine 3000 parts of dextrine,preferably a white dextrine having'a'solubility'of 85% and a fluidity at3` parts dextrlne to" 4'; parts of Water 0f |l`, and With a moistureconi'ientof4 6%, (although any otherdextrine may`beused` i`smxed withv14-,000 partso'f 95%" ethylE alcohol (10;000to 40,000 parts` and 1052parts of 18 Baum or 27% hydrochloric acid, and-converted for four hours(2te 8 hours) in a steam jacketed pressure cooker at 45 pounds pressureper squareinch (40-50' pounds.. The treatment from there on-is asdescribed in Exam'- pl'e 3 and gives an ethyl glycoside syrup having apurityv ofabout 4%- Which indicates a yield o'f about 96% on the basisof Example 3. The characteri'stics of the product are substantially' thesame as the product, of. Example 3`.

Example 5 .--E thyl glucoside syrupfrom Acles:-

trine-Refluxing method 107' paris of dextrine such;- for` example, asspecified in Exam'plef 4; i's mixed with 500 parts (40G-800 parts) 0f-95% ethyl alcohol and` 38 parts of 18 Baumer hydrochloric acid', and themixture reliuxedfor. ifi-hours ('10-24 hoursl. The subsequent-treatment:may be the same as in Examples 3 and 4. The product will be an ethylglycoside syrup containingy practically no dextrose indicating,therefore, a. yieldY of 100% on the yield basiso Example 3.

In these examples anhydrous ethyl alcohol could be used in place of`ethyl alcohol eX- cept for considerations of cost. The relativel'y largeamount ofi waterA introduced into the process withthe ethylalcohol. isrendered ineffective.. or

substantially so, in the solvolysls because of the preponderant actionof the ROH compound, the alcohol, that is, the reaction is predominantlyin Example exclusively) alcoholysis and not hydrolysis.

The products of Examples 3, 4, and 5 are noncrystallizable Syrupsbecause of the presence of the relatively large quantities of conversionproducts of alcoholysis, or alcoholysis and hydrolysis, intermediate theoriginal starch polymers and the ethyl glycosides or glycosides anddextrose resulting from the solvolysis: the situation being analogous tothat which exists in starch syrups known, commercially, as glucoses inwhich there are present products intermediate starch and dextrose.

Erample 6.-Isopr0pyl glycoside syrup from starch l 3000 parts of air drystarch is suspended in 14,000 parts of isopropyl alcohol containing 1260parts by volume of water. That is, the usual water content of commercialisopropyl alcohol is about 9% by volume. The quantity of the isopropylalcohol may vary within the range of 10.000 to 20,000 parts. With thissuspension is mixed 1050 parts of 18 Baum hydrochloric acid; orsuflicient acid to give the alcohol-acid solution an acidity between 2%and 5%. 'I'he material is treated in the same manner as indicated inExample 3 and will give an isopropyl glycoside syrup having 7% puritywhich indicates a yield of 93% on the yield basis of Example 3.

Example 7.-Propyl glycoside syrup The process is the same as in Example6 with the exception that normal propyl alcohol is used in place ofisopropyl alcohol. The product is a propyl glycoside syrup having apurity of 9% indicating a yield of 91 Example 8.--Isobutyl glycosdesyrup The process is the same as in Example 6 except that isobutylalcohol is used in place of isopropyl alcohol. coside syrup analyzing13% purity and therefore giving a yield of 87%. 'Ihe isobutyl alcohol isanhydrous.

Example 9.-.4myl glycoside syrup The process is the same as in Example 6except that Pentasol," which is a commercial mixture of various amylalcohols, is used in place of isopropyl alcohol and the pressure withinthe pressure cooker is maintained at -30 pounds instead of between and50 pounds. It is necessary to convert at the lower pressure to avoidcharring of the starch. The process gives a mixed amyl glycoside syruphaving a purity of 14% indicating a yield of 86%.

Example 10.-Isopropyl glucoside syrup from anhydrous hydrol By hydrol ismeant the mother liquor of a starch converted solution after theremoval, by crystallization, of some of the dextrose. Hydrol willordinarily have a purity of about 70%, but this purity may vary quiteconsiderably.

The hydrol is dried by distilling it with toluene. 500 parts of thedried hydrol is suspended in 2000 parts (1500 to 3500 parts) ofanhydrous isopropyl alcohol. Into this 'suspension is introduced 3% orparts of dry hydrogen chloride gas. The materal is reuxed for 60 hoursand ltered to remoye about 85 parts of the unreacted hydrol. The liquoris then neutralized with anhydrous The product is an isobutyl gluaecomo?soda. ash and iiltered. The remaining isopropyl alcohol solvent isremoved by evaporation. This yields about 400 parts of a viscousisopropyl Blycoside material.

Example 11.-Isopropyl hydrol alg/collide 51111117 bil hydrous reactionThe process is the same as in Example 10 except that an amount of Wateris used sucient to increase yields but which will be so small inproportion to the alcohol that alcoholysis predominates over hydrolysis.That is. the process can employ commercial hydrol Without drymg. andcommercial isopropyl ethyl or other alcohol containing some water; withthe result, however, that the amount of reducing sugar in the syrup willbe increased.

In the last two examples it will be possible to employ, as thecarbohydrate ingredient, converter liquors or irst greens from thedextrose process in place of hydrol, which term usually refers to amother liquor from which as much dextrose has been removed bycrystalliaztlon as is commercially feasible. The advantage of usinghydrol is that it is a relatively cheap product.

Examples b' and 1l, inclusive, also give products which are believed tobe novel as such. Their characteristics are generally similar to theproducts of Examples 3 to 5.

Example 12.*Glycoside syrup from starch by mild. conversion 2500 partsof air dry starch is mixed with 13,000 parts of ethyl alcohol and 600parts'of 18 Baume hydrochloric acid and the mixture, at an acidity ofabout 1%, is converted in a steam J'acketed pressure cooker at 25 poundssteam pressure per square inch for one hour. The pressure is thenreleased and the liquor neutralized with sodium carbonate. The liquor isthen filtered to remove unconverted starch, decolorized by the additionof 5% of Darco based on the weight of the starch, nltered again andevaporated to remove excess oi ethyl alcohol. The product is a. syrup ofethyl giycosides containing some reducing sugars; the glycoside portionconsistingof a. minor part of ethyl glucoside and a major part of ethylglycoside oi' dextrose polymers. The product differs from syrup ofExample 3 in that it contains a substantially greater proportion of highdextrose polymer glyoosides.

Example 13 Glucoside from maltose Two parts of maltose are suspended in20 parts of anhydrous methyl alcohol and dry hydrogen chloride gas isadded so that the liquor has an acidity of 3.5%. The material isreiluxed for seven hours, cooled to room temperature, crystallized for24 hours and centrifuged so as to give l part of alpha methyl glucoside.

This example is an instance of the conversion of a disaccharide for theproduction of a glucoside under anhydrous conditions. If desired watercould be added to the reaction in an amount sufcient to produce a higheryield but small enough so that the alcoholysis reaction will predominateover or exclude hydrolysis.

In place of maltose other disaccharides yielding, on hydrolysis,reducing sugars either of the aldehyde or ketone class can be employed.The disaccharides are to be regarded as polymers of reducing sugars.

It will be possible instead of using the alcohol singly to use a.mixture of alcohols.

I claim:

which comprises mixing 2500 parts of ain-dried starch with about 13,000parts of 95% ethyl alcohol and enough aqueous hydrochloric acid to givev,ethyl alcohol, and about 600 parts or laf" B, hy-

drochloric acid.

y 17. Process for the production of a non-crystallizable glycoside syrupwhich comprises reacting, at elevated temperature, a. reducingsaccharide polymer with an aliphatic compound which is at leastpartially miscible with water and which contains an alcoholic hydroxylgroup, in contact with an acid catalyst and an amount of water'suficientto promote the reaction, but small enough '8o' that alcoholysispredominates over hydrolysis.

"18; A non-crystallizable syrup resulting from reaction of a reducingsaccharide polymer with an aliphatic compound atleast partially misclhlewith water and containing 2 tov 5 carbon vatoms and an alcoholichydroxyl group,- in contact with an acid catalyst and an amount of watersuiiicient to promote the reaction but small enough so that alcoholysispredcmlnates over hydrolysis, which syrup` comprises a major portion ofglucosides and a -minor but appreciable portion of glycosides ofreducing saccharide polymers, the substituent aliphatic groups of saidglucosides and said :glycosides con-taining from 2`to 5 carbon atoms. f19. A non-crystallizable syrup resulting from reaction of starch andethyl alcohol, in contact with an acid catalyst and an amount of watersufficient to promote the reaction but small enough so that alcoholysispredominates over hydrolysis, which syrup comprises a major portion ofethyl glucoside and a minor but appreciable portion o1 ethyl glycosidesof dextrose polymers. 20. A non-crystallizable syrup resulting fromreaction of starch and amyl alcohol, in contact with an acid catalystand an amount oi water sufficient to promote the reaction but smallenough so that alcoholysis predominates over hydrolysis, which syrupcomprises a major portion of amyl glucoside and a minor but appreciableportion of amy] glycosides of dextrose polymers. 21. Anon-crystallizable syrup resulting Ifrom reaction of dextrose polymerswith an alcohol having from 2 to 5 carbon atoms, in contact with an acidcatalyst and an amount of water sufcient to promote the reaction butsmall enough so that alcoholysis predominates over hydrolysis, whichsyrup comprises a major portion of glucoin proportion to the alcohol, sothatmethanolysis escaso? -side in the form of a non-crystallizable syrupsides and a minor butappreciable portion ofglycosdes of dextrosepolymers intermediate said iirst mentioned dextrose polymersand'dextrose. the substituent aliphatic groups of said glucosides andsaid glycosides containing from 2 to 5 carbon atoms. Y

22. A non-crystallizable syrup resulting from reaction of a reducingsaccharide polymer with an aliphatic, compound at least partiallymiscible withy water and containing 2 to 5 carbon atoms and an alcoholichydroxyl group, in contact with anacid catalyst and an amount of watersufilcent to promote the reaction but small enough so that alcoholysispredominates over hydrolysis, which syrup comprises a substantialportion of glucosides and a substantial portion of glycosides oireducing saccharide polymers, the substituent aliphatic groups of said,glucosides andsald glycosidescontaini'ng from 2 to 5 carbon atoms. v,23. Ihe process Vwhich comprises: reacting-100 Darts of starch with 500to 1,000 parts of methyl alcohol and 8 parts of 18 Baum hydrochloricacid at a temperature between 150 F. and 222 F., in the presence of anamount oi watersuillcient to promote the reaction but'small enoughpredominates over hydrolysis; 'crystalllzing alpha methyl glucoside inthe liquor resulting'thereirom and separating `the crystals:neutralizing the residual mother liquor afterthe separation of thecrystals to stop the Ametluatnolysis; crystallizing alpha methyl"glucoside from said residual mother liquor and removing the crystalstherefrom; concentrating the then remaining liquor tov about Brix andcooling the same to about room temperature to bring aboutcrystallization therefro of beta methylv glucoside.

24. Non-crystallizable sirup comprising the reaction product oi' starch,and an alcohol having from 2 to 5 carbon atoms, in contact with an acidcatalyst'and an amount of water sufilcient to promote the reaction butsmall enough in comparison with the alcohol, so that alcoholysispredominates -over hydrolysis, which sirup contains a major quantity ofglucosidesand a minor quantity ofthe glycosidesof dextrose polymers,intermediate the' starch and dextrose, sufllcient to make said sirupnon-crystallizing.

25. Non-crystallizable slrup comprising the reaction product of starch,and an alcohol having from 2 to 5 carbon atoms, in contactwith an acidcatalyst and an amount of water sumcient to promote the reaction butsmall enough in comparison with -the alcohol, so that alcoholysispredominates over hydrolysis, which sirup contains a major quantity ofglucosides, a small quantity of free reducing sugar, and a smallquantity of the glycosides of dextrose polymers intermediate the starchand dextrose, sufiicient to make said sirup non-crystalllzable.

SIDNEY M. CANTOR.

